Acrylate-ureadiacetoacetamide-diacetoacetamide copolymers

ABSTRACT

Crosslinked random acrylate-ureadiacetoacetamide-diacetoacetamide copolymers are disclosed. These copolymers are prepared by the reaction of at least one polyfunctional acrylate with at least one ureadiacetoacetamide and at least one diacetoacetamide in the presence of a catalyst capable of promoting the reaction between the polyfunctional acrylate, the ureadiacetoacetamide, and the diacetoacetamide. In a preferred embodiment, the copolymers are employed to produce wear layer compositions for surface coverings.

This is a division of application Ser. No. 942,189, filed Sept. 14,1978.

This invention relates to polymers.

More specifically, this invention relates toacrylate-ureadiacetoacetamide-diacetoacetamide copolymers and tocoatings or films produced from these copolymers.

In one of its more specific aspects, this invention pertains tocrosslinked random copolymers which are the reaction products ofpolyfunctional acrylates, ureadiacetoacetamides, and diacetoacetamides.

The resilient flooring industry is continually searching for newabrasion-resistant polymeric compositions which will serve as wearlayers for decorative surface coverings, especially thermoplastic floorcoverings.

The present invention provides novelacrylate-ureadiacetoacetamide-diacetoacetamide polymers which exhibitexcellent film-forming properties and abrasion-resistant properties.Accordingly, these polymers, in film form, are well suited for use aswear layers for decorative thermoplastic floor coverings.

According to this invention, there is provided a crosslinked randomacrylate-ureadiacetoacetamide-diacetoacetamide copolymer produced by thereaction of at least one polyfunctional acrylate with at least oneureadiacetoacetamide and at least one diacetoacetamide in the presenceof a catalyst capable of promoting the reaction between thepolyfunctional acrylate, the ureadiacetoacetamide, and thediacetoacetamide.

Also, according to this invention, there is provided a thermoplasticfloor covering coated with a wear layer composition comprising acrosslinked random acrylate-ureadiacetoacetamide-diacetoacetamidecopolymer produced by the reaction of at least one polyfunctionalacrylate with at least one ureadiacetoacetamide and at least onediacetoacetamide in the presence of a catalyst capable of promoting thereaction between the polyfunctional acrylate, the ureadiacetoacetamide,and the diacetoacetamide.

It is to be understood that this invention also provides for theproduction of crosslinked acrylate-ureadiacetoacetamide copolymers, thatis, copolymers prepared by the reaction of at least one polyfunctionalacrylate with at least one ureadiacetoacetamide in the presence of acatalyst capable of promoting the reaction between the polyfunctionalacrylate and the ureadiacetoacetamide. Theseacrylate-ureadiacetoacetamide copolymers have been found to exhibitfilm-forming properties which make the copolymers suitable for use toproduce films or coatings. However, the resulting films or coatings tendto be rather hard, inflexible, and accordingly, not as well suited foruse as wear layer compositions for thermoplastic floor coverings as arethe acrylate-ureadiacetoacetamide-diacetoacetamide copolymers whichfacilitate the formation of more flexible wear layer coatings.

As the polyfunctional acrylate, use can be made of compounds having theformula

    R--O--C(O)--CH═CH.sub.2).sub.4,

    R.sup.1 --O--C(O)--CH═CH.sub.2).sub.3, or

    R.sup.2 --O--C(O)--CH═CH.sub.2).sub.2

wherein

R represents ##STR1## R¹ represents ##STR2## R² represents: a (C₁ toC₁₀) alkylene group, a (C₁ to C₄) alkyl substituted (C₁ to C₁₀) alkylenegroup, --C₂ H₄ O--_(a) --C₂ H₄ --, ##STR3## --CH₂ CH₂ CH₂ CH₂ O--_(c)CH₂ CH₂ CH₂ CH₂ --, a cycloalkylene group, a cycloalkane bearing two (C₁to C₃) alkylene groups, ##STR4## R³ represents hydrogen or (C₁ to C₃)alkyl; a is an integer from 1 to 20;

b is an integer from 1 to 10; and

c is an integer from 1 to 5.

Representative of the above useable polyfunctional acrylates aretrimethylol propane triacrylate, pentaerythritol tetraacrylate, hexanediol diacrylate, polyethylene glycol (200) diacrylate, ethylene glycoldiacrylate, tripropylene glycol diacrylate, trimethyl hexane dioldiacrylate, 1,4-cyclohexane dimethanol diacrylate, dibutylene glycoldiacrylate, 1,4-cyclohexane diacrylate, dipropylene glycoldi-2-acrylyl-ethyl ether, methylenebis(4-cyclohexane-2-acrylyl-ethylurethane) 2,2,4-trimethylhexanebis(2-acrylyl-ethyl urethane), isophoronedi(2-acrylyl-ethyl urethane), and the like.

The three above-recited urethane-containing diacrylates are not known tobe commercially available. Accordingly, Examples 17 through 19demonstrate a method for the preparation of each urethane-containingdiacrylate recited above.

As the ureadiacetoacetamide, use can be made of compounds having theformula

    H.sub.3 C--C(O)--CH.sub.2 --C(O)--NH--R.sup.4 --NH--C(O)--HN--R.sup.5 --NH--C(O)--HN--R.sup.4 --NH--C(O)--CH.sub.2 --C(O)--CH.sub.3

wherein

R⁵ represents: 2,2,4-trimethylhexamethylene,2,4,4-trimethylhexamethylene, mixtures of 2,2,4-trimethylhexamethyleneand 2,4,4-trimethylhexamethylene, methylenebis(4-cyclohexylene), and3-methylene-3,5,5-trimethylcyclohexylene;

wherein each R⁴ may be the same or different and separately represents:a (C₁ to C₁₀) alkylene group, a (C₁ to C₄) alkyl substituted (C₁ to C₁₀)alkylene group, --C₂ H₄ O--_(d) --C₂ H₄ --, ##STR5## a cycloalkylenegroup, a cycloalkane bearing two (C₁ to C₃) alkylene groups, --H₆ C₃O--C₂ H₄ O--_(e) --C₂ H₄ ----OC₃ H₆ --, ##STR6## d is an integer from 1to 6; and e is an integer from 1 to 4.

Representative of the above usable ureadiacetoacetamides are bis1,3(1-acetoacetamide-2,2,4-trimethylhexamethylene-6-ureylene)3-methylene-3,5,5-trimethylcyclohexylene(hereinafter UDA-1); bis4,4(1-acetoacetamide-2,2,4-trimethylhexamethylene-6-ureylene)1,1-methylenedicyclohexylene(hereinafter UDA-2); bis1',6'(1-acetoacetamide-2,2,4-trimethylhexamethylene-6-ureylene)2,2,4-trimethylhexamethylene(hereinafter UDA-3); bis1,6(1-acetoacetamide-1,4-dimethylenecyclohexane-4-ureylene)2,2,4-trimethylhexamethylene(hereinafter UDA-4); bis4,4-(1-acetoacetamide-1,4-dimethylenecyclohexane-4-ureylene)1,1-methylenedicyclohexylene(hereinafter UDA-5); and bis1,6-(1-acetoacetamide-1,3-dimethylenecyclohexane-4-ureylene)2,2,4-trimethylhexanemethylene(hereinafter UDA-6).

Unlike most of the polyfunctional acrylates, the ureadiacetoacetamidesare not known to be commercially available. Accordingly, suitablemethods for preparing the ureadiacetoacetamides usable in this inventionare set forth in Examples 1 through 10 below.

As the diacetoacetamide, use can be made of compounds having the formula

    R.sup.4 --NH--C(O)--CH.sub.2 --C(O)--CH.sub.3).sub.2

wherein R⁴, d, and e are as defined above.

Representative of the above usable diacetoacetamides are isophoronediacetoacetamide, diethylene glycol di-3-acetoacetamide propyl ether,N,N'-bis(propyl-3-acetoacetamide)-piperazine,1,4-cyclohexanebis(methylacetoacetamide),1,3-cyclohexanebis(methylacetoacetamide),2,2,4-trimethylhexamethylenediacetoacetamide,1,3-propanediacetoacetamide, diethyleneglycol-di-2-acetoacetamide-ethylether, dipropyleneglycol diacetoacetamide propyl ether,1,4-cyclohexanebis(acetoacetamide), trimethylhexamethylenediacetoacetamide, and the like.

The above usable diacetoacetamides are not known to be commerciallyavailable. Accordingly, suitable methods for preparing thediacetoacetamides usable in this invention are set forth in Examples 11through 16 below.

The amounts of polyfunctional acrylate, ureadiacetoacetamide, anddiacetoacetamide can be varied within relatively wide ranges.Preferably, about 1 to about 2 moles of polyfunctional acrylate areemployed for every mole of total ureadiacetoacetamide anddiacetoacetamide. Best results are usually obtained in a mole ratio offrom about 1.2 to about 1.4 moles of polyfunctional acrylate to about 1mole of total ureadiacetoacetamide and diacetoacetamide. Preferably, the1 mole of total ureadiacetoacetamide and diacetoacetamide will compriseureadiacetoacetamide in an amount of from about 0.1 mole to about 0.9mole and diacetoacetamide in an amount of from about 0.1 mole to about0.9 mole.

Although the ureadiacetoacetamides and the diacetoacetamides can beseparately prepared, it is preferred, as demonstrated in Examples 1-10,that both ureadiacetoacetamide and diacetoacetamide be prepared in asingle reaction rather than being prepared by separate reactions.

As the catalyst to promote the reaction, a Michael reaction, use can bemade of any of a variety of well known Michael reaction-type catalystscommonly employed to promote condensation. Particularly suitable arestrong basic catalysts such as sodium methoxide, sodium metal, sodiumethylate, benzyl-trimethyl ammonium methoxide, and the like. Catalyticamounts of materials are selected in accordance with well knownpractices in the polymer art, the amount being one sufficient to promotethe polycondensation reaction. For further information relating to theMichael reaction mechanism, see "The Michael Reaction" by E. D. Bergmannet al., Organic Reactions, Vol. 10, chapter 3, pages 179-555, and ModernSynthetic Reactions, H. O. House, 2nd Ed. (1972), pages 595-623, bothherein incorporated by reference.

The polymerization reaction can be carried out using the reactants asthe only reaction medium since both the polyfunctional acrylates, theureadiacetoacetamides, and the diacetoacetamides are normally in theliquid state and/or they can be uniformly blended together.

Further, if the acrylate-ureadiacetoacetamide-diacetoacetamide copolymeris employed to produce a wear layer composition, the polymerizationreaction can be carried out in the presence of art recognized amounts ofoptional ingredients typically employed in wear layer compositions suchas surfactants, heat and light stabilizers, and the like.

The following examples will serve to more fully illustrate specificembodiments of and the best mode for practicing this invention.

EXAMPLE 1

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide.

To a reaction vessel were added about 17 grams (0.065 mole) of methylenebis-4-cyclohexyl isocyanate (designated "Hylene W" commerciallyavailable from E. I. DuPont) in about 30 milliliters of methylenechloride and about 58 grams (0.39 mole) of 2,2,4-trimethylhexanediaminein about 260 milliliters of methylene chloride with stirring.

The contents of the reaction vessel were cooled to and maintained at atemperature of from 10° to 15° C. and about 55 grams (0.65 mole) ofdiketene were added to the contents of the reaction vessel with coolingto 5° to 10° C.

The contents of the reaction vessel were held at a temperature of from5° to 15° C. for about 41/2 hours and then about 6 grams ofisopropylamine were added to the contents of the reaction vessel.

The resulting reaction product was transferred to a separatory funneland acidified with dilute hydrochloric acid.

The reaction product was washed twice, once with about 250 millilitersof water and about 50 milliliters of saturated sodium chloride solutionand a second time with about 250 milliliters of water, about 50milliliters of saturated sodium chloride solution and a sufficientamount (about 5 cc) of saturated NaHCO₃ solution to neutralize theseparatory funnel contents to a pH of about 6.

After the second washing, the methylene chloride layer containing thereaction product was dried with anhydrous magnesium sulfate. Themagnesium sulfate was filtered off; the methylene chloride removed byvacuum distillation, and the resulting product observed, analyzed, andfound to be a light yellow viscous mixture of 0.2 mole of UDA-2 and 0.8mole of trimethylhexanediacetoacetamide. The yield was 119.4 grams.

EXAMPLE 2

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide.

To a reaction vessel were added about 9.7 grams (0.044 mole) isophoronediisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate) inabout 25 milliliters of methylene chloride and about 44.3 grams (0.3mole) trimethylhexanediamine in about 230 milliliters of methylenechloride with stirring.

The contents of the reaction vessel were cooled to and maintained at atemperature of from 10° to 15° C. and about 41.3 grams (0.49 mole) ofdiketene were added to the contents of the reaction vessel with coolingto about 10° C.

The contents of the reaction vessel were held at about 10° C. for about3 hours.

The resulting reaction product was transferred to a separatory funneland acidified with dilute hydrochloric acid.

The reaction product was washed twice, once with about 250 millilitersof water and about 50 milliliters of saturated sodium chloride solutionand a second time with about 250 milliliters of water, about 50milliliters of saturated sodium chloride solution and a sufficientamount (about 5 cc) of saturated NaHCO₃ solution to neutralize theseparatory funnel contents to a pH of about 6.

After the second washing, the methylene chloride layer containing thereaction product was dried with anhydrous magnesium sulfate. Themagnesium sulfate was filtered off; the methylene chloride removed byvacuum distillation, and the resulting product observed, analyzed, andfound to be a light yellow viscous mixture of 0.2 mole of UDA-1 and 0.8mole of trimethylhexanediacetoacetamide. The yield was 84.5 grams.

EXAMPLE 3

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

26 grams (0.12 mole) trimethylhexane diisocyanate (TMDI) in 70milliliters CH₂ Cl₂

63 grams (0.43 mole) trimethylhexanediamine (TMDA) in 300 millilitersCH₂ Cl₂

55.5 grams (0.66 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.3 mole of UDA-3 and 0.7 mole oftrimethylhexanediacetoacetamide. The yield was 134.2 grams.

EXAMPLE 4

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

26 grams (0.12 mole) trimethylhexanediisocyanate (TMDI) in 50milliliters CH₂ Cl₂

44.4 grams (0.31 mole) trimethylhexanediamine (TMDA) in 210 millilitersCH₂ Cl₂

33.6 grams (0.40 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzed,and found to contain 0.5 mole of UDA-3 and 0.5 mole oftrimethylhexanediacetoacetamide. The yield was 96 grams.

EXAMPLE 5

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

31.2 grams (0.15 mole) trimethylhexanediisocyanate (TMDI) in 50milliliters CH₂ Cl₂

41.5 grams (0.28 mole) trimethylhexanediamine (TMDA) in 200 millilitersCH₂ Cl₂

28.2 grams (0.34 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.75 mole of UDA-3 and 0.25 mole oftrimethylhexanediacetoacetamide. The yield was 105 grams.

EXAMPLE 6

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

8.7 grams (0.034 mole) "Hylene W" (methylene bis-4-cyclohexylisocyanate) in 20 milliliters CH₂ Cl₂

30.8 grams (0.21 mole) trimethylhexanediamine (TMDA) in 135 millilitersCH₂ Cl₂

27.3 grams (0.33 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.2 mole of UDA-2 and 0.8 mole oftrimethylhexanediacetoacetamide. The yield was 69.6 grams.

EXAMPLE 7

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

18.2 grams (0.086 mole) trimethylhexanediisocyanante (TMDI) in 20milliliters CH₂ Cl₂

10.7 grams (0.07 mole) trimethylhexanediamine and

19.9 grams (0.14 mole) 1,3-cyclohexylbismethylamine in 200 millilitersCH₂ Cl₂

13.8 grams (0.09 mole) trimethylhexanediamine

39.4 grams (0.47 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.3 mole mixed UDA-3 and UDA-6 and 0.7 mole oftrimethylhexanediacetoacetamide. The yield was 95 grams.

EXAMPLE 8

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

26 grams (0.12 mole) trimethylhexanediisocyanate (TMDI) in 50milliliters CH₂ Cl₂

19.8 grams (0.13 mole) trimethylhexanediamine and

14.3 grams (0.10 mole) 1,4-cyclohexylbismethylamine in 200 millilitersCH₂ Cl₂

24.8 grams (0.27 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.75 mole of mixed UDA-3 and UDA-4 and 0.25 mole oftrimethylhexanediacetoacetamide. The yield was 83 grams.

EXAMPLE 9

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

26 grams (0.10 mole) "Hylene W" (methylene bis-4-cyclohexylisocyanate)in 40 milliliters CH₂ Cl₂

18.5 grams (0.13 mole) trimethylhexanediamine and

14.2 grams (0.10 mole) 1,4-cyclohexylbismethylamine in 500 millilitersCH₂ Cl₂

80.2 grams (0.54 mole) trimethylhexanediamine

114.4 grams (1.36 mole) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.15 mole of mixed UDA-2 and UDA-5 and 0.85 mole oftrimethylhexanediacetoacetamide. The yield was 250 grams.

EXAMPLE 10

This example demonstrates the preparation of a mixture containingureadiacetoacetamide and diacetoacetamide using the followingingredients and substantially the procedure of Example 1.

Ingredients

31 grams (0.12 mole) "Hylene W" (methylene bis-4-cyclohexylisocyanate)in 50 milliliters CH₂ Cl₂

136 grams (0.92 mole) 2,2,4-trimethylhexamethylenediamine in 250milliliters CH₂ Cl₂

137 grams (1.63 moles) diketene

The resulting reaction product was viscous, yellow in color, analyzedand found to contain 0.15 mole of UDA-2 and 0.85 mole oftrimethylhexamethylenediacetoacetamide. The yield was 276 grams.

EXAMPLE 11

This example demonstrates a method for the preparation of isophoronediacetoacetamide.

About 85 grams (0.5 mole) of isophorone diamine (3-aminomethyl3,5,5-trimethylcyclohexylamine) and about 325 milliliters of methylenechloride were added to a reaction vessel with stirring.

The contents of the reaction vessel were cooled to and maintained at atemperature of about 15° C. and about 80 grams (0.95 mole) of diketenewere added to the contents of the reaction vessel over a period of about1 hour.

The temperature of the contents of the reaction vessel was held at about15° C. for about 13/4 hours and the resulting reaction product wastransferred to a separatory funnel and acidified with dilutehydrochloric acid.

The reaction product was washed twice, once with about 250 millilitersof water and about 50 milliliters of saturated sodium chloride solutionand a second time with about 250 milliliters of water, about 50milliliters of saturated sodium chloride solution and a sufficientamount (about 5 cc) of saturated NaHCO₃ solution to neutralize theseparatory funnel contents to a pH of about 6.

After the second washing, the methylene chloride layer containing thereaction product was dried with anhydrous magnesium sulfate. Themagnesium sulfate was filtered off; the methylene chloride was removedby vacuum distillation and the resulting product, isophoronediacetoacetamide, was recovered in a yield of about 132 grams andobserved to be viscous and light yellow in color.

EXAMPLE 12

This example demonstrates a method for the preparation ofdiethyleneglycol diacetoacetamide propyl ether.

About 66 grams (0.3 mole) of diethyleneglycol diaminopropyl ether(commercially available from Union Carbide Corporation, designated"Polyglycoldiamine H-221") and about 230 milliliters of methylenechloride were added to a reaction vessel with stirring.

The contents of the reaction vessel were cooled to and maintained at atemperature of about 15° C. and about 50.4 grams (0.6 mole) of diketenewere added to the contents of the reaction vessel over a period of about1 hour.

The temperature of the contents of the reaction vessel was held at about10° to 15° C. for a period of about 4 hours and the methylene chloridewas removed by vacuum distillation.

The resulting reaction product was dissolved in isopropyl alcohol andrecrystallized from the alcohol. The resulting product, diethyleneglycoldiacetoacetamide propyl ether, was recovered and found to have a meltingpoint range of about 62° to 63° C. and observed to be white in color.

EXAMPLE 13

This example demonstrates a method for the preparation ofN,N'-bis(propyl-3-acetoacetamide)-piperazine.

The following ingredients were reacted using substantially the procedureof Example 11 with the exception that the contents of the reactionvessel were held at 10° to 15° C. for a period of about 4 hours insteadof the 13/4 hours in Example 11.

    ______________________________________                                        Ingredients         Amount                                                    ______________________________________                                        diketene            50.4 grams (0.6 mole)                                     N,N'-bis(aminopropyl)-piperazine                                                                  60 grams (0.3 mole)                                       methylene chloride  250 milliliters                                           ______________________________________                                    

The resulting product, N,N'-bis(propyl-3-acetoacetamide)-piperazine, wasrecovered in a yield of about 92 grams and observed to be viscous andlight yellow in color.

EXAMPLE 14

This example demonstrates a method for the preparation of1,4-cyclohexanebis(methylacetoacetamide).

The following ingredients were reacted using substantially the procedureof Example 12 with the exception that the contents of the reactionvessel were held at about 15° C. for about 2 hours.

    ______________________________________                                        Ingredients         Amount                                                    ______________________________________                                        diketene            33.6 grams (0.4 mole)                                     1,4 cyclohexanebis(methylamine)                                                                   28.4 grams (0.2 mole)                                     methylene chloride  100 milliliters                                           ______________________________________                                    

The resulting crude product, 1,4-cyclohexanebis(methylacetoacetamide),was recovered and recrystallized from isopropyl alcohol. Therecrystallized product was found to have a melting point range of about140° to 143° C. and observed to be white in color.

EXAMPLE 15

This example demonstrates a method for the preparation of1,3-cyclohexanebis(methylacetoacetamide).

The following ingredients were reacted using substantially the procedureof Example 12 with the exception that chloroform was substituted for themethylene chloride, and rather than recrystallizing in isopropylalcohol, the reaction product was washed in benzene.

    ______________________________________                                        Ingredients         Amount                                                    ______________________________________                                        diketene            84 grams (1 mole)                                         1,3-cyclohexanebis(methylamine)                                                                   71 grams (0.5 mole)                                       chloroform          250 milliliters                                           ______________________________________                                    

The benzene insoluble fraction of the reaction product was recovered as1,3-cyclohexanebis(methylacetoacetamide) and found to have a meltingpoint range of about 105° to 115° C. and observed to be light yellow incolor.

EXAMPLE 16

This example demonstrates a method for the preparation of2,2,4-trimethylhexamethylenediacetoacetamide.

The following ingredients were reacted using substantially the procedureof Example 11 with the exception that the contents of the reactionvessel were held at 10° to 15° C. for a period of about 2 hours insteadof the 13/4 hours in Example 11.

    ______________________________________                                        Ingredients        Amount                                                     ______________________________________                                        diketene           49.2 grams (0.59 mole)                                     trimethylhexanediamine                                                                           45.3 grams (0.31 mole)                                     methylene chloride 150 milliliters                                            ______________________________________                                    

The resulting product, 2,2,4-trimethylhexamethylenediacetoacetamide, wasrecovered in a yield of about 89 grams and observed to be light yellowin color and viscous.

EXAMPLE 17

This example demonstrates the preparation of a urethane-containingdiacrylate.

About 1 mole of methylenebis-4-cyclohexane isocyanate (designated"Hylene W", commercially available from E. I. DuPont de Nemours Co.) andabout 2 moles of hydroxyethylacrylate and about 0.05 gram of dibutyltindilaurate catalyst were added to a reaction vessel at room temperature,with stirring. The temperature of the reaction vessel was increased toabout 60° C. After about 3 hours, the resulting reaction product,methylenebis(4-cyclohexane-2-acryl-ethyl urethane), having the formula##STR7## was recovered.

EXAMPLE 18

This example demonstrates the preparation of a urethane-containingdiacrylate.

About 1 mole of 2,2,4-trimethylhexane diisocyanate (designated "TMDI",commercially available from Thorson Chemical Co.) and about 2 moles ofhydroxyethylacrylate and about 0.05 gram of dibutyltin dilauratecatalyst were added to a reaction vessel at room temperature, withstirring. The temperature of the reaction vessel was increased to about60° C. After about 3 hours, the resulting reaction product,2,2,4-trimethylhexane-bis(2-acrylyl-ethyl urethane), having the formula##STR8## was recovered.

EXAMPLE 19

This example demonstrates the preparation of a urethane-containingdiacrylate.

About 1 mole of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate(designated "IPDI" isophorone diisocyanate, commercially available fromThorson Chemical Co.) and about 2 moles of hydroxyethylacrylate andabout 0.05 gram of dibutyltin dilaurate catalyst were added to areaction vessel at room temperature, with stirring. The temperature ofthe reaction vessel was increased to about 60° C. After about 3 hours,the resulting reaction product, isophorone di(2-acrylyl-ethyl urethane),having the formula ##STR9## was recovered.

EXAMPLE 20

This example demonstrates the preparation of a polymer film of thisinvention.

About 1.2 moles of hexanediol diacrylate, about 1.0 molediacetoacetamide of the reaction product mixture of Example 1 (contains0.2 mole UDA-2), about 0.4 percent by weight of the reactants of a 30%by weight polyethyleneoxide siloxane surfactant (Dow Corning DC-193) inmethanol solution and about 0.3 percent by weight of the reactants of a15% by weight sodium methoxide in methanol catalyst solution were addedto a reaction vessel at room temperature with stirring.

The resulting polymer mixture was coated on a glass surface using a Birdapplicator to a coating thickness of about 0.003 inch.

The coating was non-tacky after about 1 hour and was allowed to cure forabout 16 hours at a temperature of about 60° C.

The resulting cured polymer film was removed from the glass surface andobserved to be clear and colorless. The film was tested by differentialscanning calorimetery (DuPont 900 Thermal Analyzer) and found to have aTg midpoint of about 36° C. The cured polymer film was also found tohave a tensile strength of 3,330 psi and a percent elongation of 171.

EXAMPLE 21

The following ingredients were reacted using substantially the procedureof Example 20.

    ______________________________________                                        Ingredients              Amount                                               ______________________________________                                        hexanediol diacrylate    1.4 moles                                            reaction product mixture of Example 1                                                                  1.0 mole                                             30% by weight "DC-193" in methanol solution                                                            0.4% by weight                                       15% by weight sodium methoxide in methanol                                                             0.3% by weight                                       catalyst solution                                                             ______________________________________                                    

The resulting mixture was coated on a glass surface and cured at about60° C. for about 16 hours.

The resulting cured polymer film was removed from the glass surface andobserved to be clear and colorless. The film was tested and found tohave a Tg midpoint of about 42° C. The polymer film was also found tohave a tensile strength of 4,150 psi and a percent elongation of 108.

EXAMPLE 22

The following ingredients were reacted using substantially the procedureof Example 20.

    ______________________________________                                        Ingredients              Amount                                               ______________________________________                                        hexanediol diacrylate    1.6 moles                                            reaction product mixture of Example 1                                                                  1.0 mole                                             30% by weight "DC-193" in methanol solution                                                            0.4% by weight                                       15% by weight sodium methoxide in methanol                                                             0.3% by weight                                       catalyst solution                                                             ______________________________________                                    

The resulting mixture was coated on a glass surface and cured at about60° C. for about 16 hours.

The resulting cured polymer film was removed from the glass surface andobserved to be clear and colorless. The film was tested and found tohave a Tg midpoint of about 44° C. The polymer film was also found tohave a tensile strength of 2,890 psi and a percent elongation of 30.

The following Table I contains Examples 23 through 25. All polymercompositions were prepared using substantially the procedure of Example20. All examples were catalyzed with 1 percent by weight of a 15 percentby weight sodium methoxide in methanol solution and included 0.4 percentby weight of a 30 percent by weight "DC-193" in methanol solutionsurfactant.

                                      TABLE I                                     __________________________________________________________________________    Cured Polymer Films of 1.0 Mole of the                                        Reaction Product Mixture of Example 1 (U-1) With                              Hexanediol Diacrylate (HDDA) and -Tripropyleneglycol Diacrylate (TPGDA)                                        Tensile                                      Example                    Tg (DSC)                                                                            Strength                                                                           Percent                                 No.  Ingredients and Amount (Moles)                                                                      Midpoint                                                                            PSI  Elongation                              __________________________________________________________________________    23   1.0M                                                                             U-1                                                                              1.2M                                                                             HDDA .2M                                                                              TPGDA                                                                              37°                                                                          2,770                                                                              113                                     24   1.0M                                                                             "  1.0M                                                                             "    .4M                                                                              "    32°                                                                          2,420                                                                              163                                     25   1.0M                                                                             "   .8M                                                                             "    .6M                                                                              "    23°                                                                          1,410                                                                              241                                     __________________________________________________________________________

The following Table II contains Examples 26 and 27. Both polymercompositions were prepared using substantially the procedure of Example20. Both examples were catalyzed with 1 percent by weight of a 15percent by weight sodium methoxide in methanol solution and included 0.4percent by weight of a 30 percent by weight "DC-193" in methanolsolution surfactant.

                  TABLE II                                                        ______________________________________                                        Cured Polymer Films of 1.0 Mole of the                                        Reaction Product Mixture of Example 3 (U-3) With                              Hexanediol Diacrylate (HDDA)                                                                          Tg             Per-                                   Ex-                     (DSC)   Tensile                                                                              cent                                   ample Ingredients and   Mid-    Strength                                                                             Elon-                                  No.   Amount (Moles)    point   PSI    gation                                 ______________________________________                                        26    1.0M   U-3    1.2M HDDA   37°                                                                          1,490  309                              27    1.0M   "      1.4M "      33°                                                                          1,940  241                              ______________________________________                                    

The following Table III contains Examples 28 through 32. All polymercompositions were prepared using substantially the procedure of Example20. All examples were catalyzed with 1 percent by weight of a 15 percentby weight sodium methoxide in methanol solution and included 0.4 percentby weight of a 30 percent by weight "DC-193" in methanol solutionsurfactant.

                                      TABLE III                                   __________________________________________________________________________    Cured Polymer Films of 1.0 Mole of the                                        Reaction Product Mixture of Example 4 (U-4) With                              Hexanediol Diacrylate (HDDA) and                                              Tripropyleneglycol Diacrylate (TPGDA)                                                                          Tensile                                      Example                    Tg (DSC)                                                                            Strength                                                                           Percent                                 No.  Ingredients and Amount (Moles)                                                                      Midpoint                                                                            PSI  Elongation                              __________________________________________________________________________    28   1.0M                                                                             U-4                                                                              1.2M                                                                             HDDA         30°                                                                          2,920                                                                              200                                     29   1.0M                                                                             "  1.4M                                                                             "            21°                                                                          2,670                                                                              132                                     30   1.0M                                                                             "  1.6M                                                                             "            41°                                                                          2,890                                                                               11                                     31   1.0M                                                                             "  1.2M                                                                             "    .2M                                                                              TPGDA                                                                              32°                                                                          3,850                                                                              167                                     32   1.0M                                                                             "  1.0M                                                                             "    .4M                                                                              "    31°                                                                          3,550                                                                              244                                     __________________________________________________________________________

The following Table IV contains Examples 33 through 38. All polymercompositions were prepared using substantially the procedure of Example20. All examples were catalyzed with 1 percent by weight of a 15 percentby weight sodium methoxide in methanol solution and included 0.4 percentby weight of a 30 percent by weight "DC-193" in methanol solutionsurfactant.

                                      TABLE IV                                    __________________________________________________________________________    Cured Polymer Films of 1.0 Mole of the                                        Reaction Product Mixture of Example 5 (U-5) With                              Hexanediol Diacrylate (HDDA),                                                 Tripropyleneglycol Diacrylate (TPGDA), and                                    Polyethyleneglycol Diacrylate (PEG200DA)                                                                         Tensile                                    Example                      Tg (DSC)                                                                            Strength                                                                           Percent                               No.  Ingredients and Amount (Moles)                                                                        Midpoint                                                                            PSI  Elongation                            __________________________________________________________________________    33   1.0M                                                                             U-5                                                                              1.4M                                                                             HDDA           44°                                                                          3,290                                                                               60                                   34   1.0M                                                                             "  1.2M                                                                             "    .2M                                                                              TPGDA  37°                                                                          3,740                                                                              131                                   35   1.0M                                                                             "   .8M                                                                             "    .4M                                                                              "      36°                                                                          3,670                                                                              177                                   36   1.0M                                                                             "  1.2M                                                                             "    .2M                                                                              PEG200DA                                                                             36°                                                                          4,100                                                                              172                                   37   1.0M                                                                             "  1.0M                                                                             "    .4M                                                                              "      32°                                                                          3,990                                                                              210                                   38   1.0M                                                                             "   .8M                                                                             "    .6M                                                                              "      31°                                                                          4,100                                                                              263                                   __________________________________________________________________________

EXAMPLE 39

This example demonstrates the preparation of a polymer film of thisinvention using the reaction product mixture of Example 7. About 3.5grams of the reaction product mixture of Example 7, about 2.6 gramshexanediol diacrylate, about 1 gram methanol, about 0.03 gram 30% DC-193in methanol and about 0.06 gram 15% sodium methoxide in methanol wereadded to a reaction vessel at room temperature, with stirring.

A 0.003" film of the resulting polymer mixture was drawndown on a glassplate and cured 16 hours at 60°.

The resulting cured film was stripped from the glass and was observed tobe clear and glossy. The cured film was tested and found to have atensile strength of 2,600 psi, a percent elongation of 72% and a Tgrange of 28°-48° with a midpoint of 38°. The film was found to be fairlyresistant to scratching by steel wool.

The following Table V contains Examples 40 through 42. All polymercompositions were prepared using substantially the procedure of Example20. All examples were catalyzed with 1 percent by weight of a 15 percentby weight sodium methoxide in methanol solution and included 0.4 percentby weight of a 30 percent by weight "DC-193" in methanol solutionsurfactant.

                                      TABLE V                                     __________________________________________________________________________    Cured Polymer Films of 1.0 Mole of the                                        Reaction Product Mixture of Example 8 (U-8) With                              Hexanediol Diacrylate (HDDA) and                                              Polyethyleneglycol 200 Diacrylate (PEG200DA)                                                                     Tensile                                    Example                      Tg (DSC)                                                                            Strength                                                                           Percent                               No.  Ingredients and Amount (Moles)                                                                        Midpoint                                                                            PSI  Elongation                            __________________________________________________________________________    40   1.0M                                                                             U-8                                                                              1.2M                                                                             HDDA .2M                                                                              PEG200DA                                                                             39°                                                                          4,200                                                                               31                                   41   1.0M                                                                             "  1.0M                                                                             "    .4M                                                                              "      35°                                                                          4,360                                                                              179                                   42   1.0M                                                                             "   .8M                                                                             "    .6M                                                                              "      34°                                                                          3,990                                                                              149                                   __________________________________________________________________________

EXAMPLE 43

This example demonstrates the preparation of a polymer film of thisinvention using the reaction product mixture of Example 2. About 5.3grams of the reaction product mixture of Example 2, about 3.8 gramshexanediol diacrylate, about 0.5 grams isopropyl alcohol, about 0.04gram 30% DC-193 in methanol and about 0.07 gram 40%benzyltrimethylammonium methoxide in methanol were added to a reactionvessel at room temperature, with stirring.

A 0.003" film of the resulting polymer mixture was drawndown on a glassplate and cured 16 hours at 60°.

The resulting cured film was stripped from the glass and was observed tobe inflexible, glossy, and yellow in color. The cured film was testedand found to have a Tg range of 31°-51° with a Tg midpoint of 41° andwas found to be fairly resistant to scratching by steel wool.

EXAMPLE 44

This example demonstrates the preparation of a thermoplastic floorcovering which was coated with a wear layer composition comprising across-linked random acrylate-ureadiacetoacetamide-diacetoacetamidecopolymer of this invention.

About 11.9 grams of hexanediol diacrylate, about 15.1 grams of thereaction product mixture of Example 1 and 0.19 gram of a 40% by weightbenzyltrimethyl ammonium methoxide in methanol catalyst solution wereadded to a mixing vessel with stirring at room temperature.

The resulting wear layer composition was applied using a conventionalapplicator, in this example a Bird applicator, to a 12"×12" white vinyltile and cured at 60° C. for about 16 hours.

The resulting cured acrylate-ureadiacetoacetamide-diacetoacetamidecopolymer wear layer on the tile was observed to be clear and colorless.

The wear layer coated tile was tested for gloss retention using an artrecognized traffic wheel test. The initial gloss value, before testing,was 90. After 30 minutes of testing, the gloss value was 73. After 60minutes of testing, the gloss value was 71. And after 90 minutes oftesting, the gloss value was 71. The wear layer was also subjected to anart recognized steel wool scratch test and found to exhibit good scratchresistance.

It will be evident from the foregoing that various modifications can bemade to the present invention. Such, however, are considered as beingwithin the scope of this invention.

What is claimed is:
 1. A thermoplastic floor covering coated with a wearlayer composition comprising a cross-linked randomacrylate-ureadiacetoacetamide-diacetoacetamide copolymer produced by thereaction of at least one polyfunctional acrylate with at least oneureadiacetoacetamide and at least one diacetoacetamide in the presenceof a catalyst capable of promoting the reaction between thepolyfunctional acrylate, the ureadiacetoacetamide, and thediacetoacetamide.
 2. The thermoplastic floor covering of claim 1 inwhich said polyfunctional acrylate has the formula

    R(O--C(O)--CH═CH.sub.2).sub.4

wherein R represents ##STR10##
 3. The thermoplastic floor covering ofclaim 1 in which said polyfunctional acrylate has the formula

    R.sup.1 --O--C(O)--CH═CH.sub.2).sub.3

wherein R¹ represents ##STR11## and R₃ represents hydrogen or (C₁ to C₃)alkyl.
 4. The thermoplastic floor covering of claim 1 in which saidpolyfunctional acrylate has the formula

    R.sup.2 --O--C(O)--CH═CH.sub.2).sub.2

wherein R² represents: a (C₁ to C₁₀) alkylene group, a (C₁ to C₄) alkylsubstituted (C₁ to C₁₀) alkylene group, --C₂ H₄ O--_(a) --C₂ H₄ --,##STR12## --CH₂ CH₂ CH₂ CH₂ O--_(c) CH₂ CH₂ CH₂ CH₂ --, a cycloalkylenegroup, a cycloalkane bearing two (C₁ to C₃) alkylene groups, ##STR13## ais an integer from 1 to 20; b is an integer from 1 to 10; and c is aninteger from 1 to
 5. 5. The thermoplastic floor covering of claim 1 inwhich said ureadiacetoacetamide has the formula

    H.sub.3 C--C(O)--CH.sub.2 --C(O)--NH--R.sup.4 --NH--C(O)--HN--R.sup.5 --NH--C(O)--HN--R.sup.4 --NH--C(O)--CH.sub.2 --C(O)--CH.sub.3

wherein R⁵ represents: 2,2,4-trimethylhexamethylene,2,4,4-trimethylhexamethylene, mixtures of 2,2,4-trimethylhexamethyleneand 2,4,4-trimethylhexamethylene, methylenebis(4-cyclohexylene), and3-methylene-3,5,5-trimethylcyclohexylene; wherein each R⁴ may be thesame or different and separately represents: a (C₁ to C₁₀) alkylenegroup, a (C₁ to C₄) alkyl substituted (C₁ to C₁₀) alkylene group, --C₂H₄ O--_(d) --C₂ H₄ --, ##STR14## a cycloalkylene group, a cycloalkanebearing two (C₁ to C₃) alkylene groups, --H₆ C₃ O--C₂ H₄ O--_(e) --C₂ H₄----OC₃ H₆ --, ##STR15## d is an integer from 1 to 6; and e is aninteger from 1 to
 4. 6. The thermoplastic floor covering of claim 1 inwhich said diacetoacetamide has the formula

    R.sup.4 --NH--C(O)--CH.sub.2 --C(O)--CH.sub.3).sub.2

wherein R⁴, d, and e are as defined above.
 7. The thermoplastic floorcovering of claim 1 wherein from about 1 to about 2 moles ofpolyfunctional acrylate are employed for every 1 mole of totalureadiacetoacetamide and diacetoacetamide, wherein said 1 mole comprisesureadiacetoacetamide in an amount of from about 0.1 to about 0.9 mole.8. A thermoplastic floor covering coated with a wear layer compositioncomprising a cross-linked acrylate-ureadiacetoacetamide copolymerproduced by the reaction of at least one polyfunctional acrylate with atleast one ureadiacetoacetamide in the presence of a catalyst capable ofpromoting the reaction between the polyfunctional acrylate and theureadiacetoacetamide.
 9. The thermoplastic floor covering of claim 8 inwhich said polyfunctional acrylate has the formula

    R(O--C(O)--CH═CH.sub.2).sub.4

wherein R represents ##STR16##
 10. The thermoplastic floor covering ofclaim 8 in which said polyfunctional acrylate has the formula

    R.sup.1 --O--C(O)--CH═CH.sub.2).sub.3

wherein R¹ represents ##STR17## and R₃ represents hydrogen or (C₁ to C₃)alkyl.
 11. The thermoplastic floor covering of claim 8 in which saidpolyfunctional acrylate has the formula

    R.sup.2 --O--C(O)--CH═CH.sub.2).sub.2

wherein R² represents: a (C₁ to C₁₀) alkylene group, a (C₁ to C₄) alkylsubstituted (C₁ to C₁₀) alkylene group, --C₂ H₄ O--_(a) --C₂ H₄ --,##STR18## --CH₂ CH₂ CH₂ CH₂ O--_(c) CH₂ CH₂ CH₂ CH₂ --, a cycloalkylenegroup, a cycloalkane bearing two (C₁ to C₃) alkylene groups, ##STR19## ais an integer from 1 to 20; b is an integer from 1 to 10; and c is aninteger from 1 to
 5. 12. The thermoplastic floor covering of claim 8 inwhich said ureadiacetoacetamide has the formula

    H.sub.3 C--C(O)--CH.sub.2 --C(O)--NH--R.sup.4 --NH--C(O)--HN--R.sup.5 --NH--C(O)--HN--R.sup.4 --NH--C(O)--CH.sub.2 --C(O)--CH.sub.3

wherein R⁵ represents: 2,2,4-trimethylhexamethylene,2,4,4-trimethylhexamethylene, mixtures of 2,2,4-trimethylhexamethyleneand 2,4,4-trimethylhexamethylene, methylenebis(4-cyclohexylene), and3-methylene- 3,5,5-trimethylcyclohexylene; wherein each R⁴ may be thesame or different and separately represents: a (C₁ to C₁₀) alkylenegroup, a (C₁ to C₄) alkyl substituted (C₁ to C₁₀) alkylene group, --C₂H₄ O--_(d) --C₂ H₄ --, ##STR20## a cycloalkylene group, a cycloalkanebearing two (C₁ to C₃) alkylene groups, --H₆ C₃ O--C₂ H₄ O--_(e) --C₂ H₄----OC₃ H₆ --, ##STR21## d is an integer from 1 to 6; and e is aninteger from 1 to
 4. 13. The thermoplastic floor covering of claim 8wherein said polyfunctional acrylate is reacted with theureadiacetoacetamide in a mole ratio of from about 1 to about 2 moles ofpolyfunctional acrylate to about 1 mole of ureadiacetoacetamide.
 14. Thethermoplastic floor covering of claim 8 wherein said polyfunctionalacrylate is reacted with the ureadiacetoacetamide in a mole ratio offrom about 1.2 to about 1.4 moles of polyfunctional acrylate to about 1mole of ureadiacetoacetamide.